CN1091757A

CN1091757A - Additive for polymer compositions

Info

Publication number: CN1091757A
Application number: CN93107640A
Authority: CN
Inventors: L·布安; D·劳林
Original assignee: Baxter International Inc
Current assignee: Baxter International Inc
Priority date: 1992-05-27
Filing date: 1993-05-27
Publication date: 1994-09-07
Anticipated expiration: 2013-05-27
Also published as: IL105742A0; DE69322238D1; JP3172921B2; CN1041424C; IL105742A; WO1993024563A1; CA2113814C; KR100276991B1; ZA933628B; EP0598872A1; JPH06509837A; DE69322238T2; SG70548A1; CA2113814A1; EP0598872B1

Abstract

The invention provides a kind of additive system that is used for vinyl chloride polymer formulations, the functional performance of the medical product that makes with the processibility of improving this prescription with by this prescription.With regard to the desired product performance made from regard to the thermostability of fusion manufacturing and this polymer formulators and by such material of product, this additive system shockingly is better than the system of previously known.Additive system of the present invention preferentially comprises the cooperating of optimum quantity of zinc salt main stabilizer and epoxide co-stabilizer and polyethylene external lubricant, also can comprise such as alkali, oxidation inhibitor and internal lubricant these other processing aid and performance additive.This additive system can be used for plastifying or unplasticizied vinyl chloride polymer formulations.

Description

Additive for polymer compositions

The present invention relates to be used for the vinyl chloride polymer formulations of medicinal use, or rather, the present invention relates to the flexibility that is used for medical sterilization equipment that makes by this prescription, the stability of plasticity vinyl chloride polymer formulations.

Various polymer formulators can be used for producing extruding and layered product, as flexible cell, and tubular equipment and injection-molded item.For example, flexible cell and tubular equipment can be applicable to medicine industry, are particularly useful for splendid attire and transport parenteral solution, for example intravenous solution, dialysis solution, medicine and medicament, nutritive medium, the respiratory therapy product, the product of blood, blood plasma and other relevant blood.When being used for medicine industry, these products usually splendid attire or contact join intravital fluid of patient or solid.Therefore these equipment must be substantial transparent, softish, essentially no extract, do not absorb by the fluid of splendid attire or solid, do not have particulate matter basically, and the product of splendid attire is remained under the sterilising conditions be used or remove until this product.By these containers that this plastic material is made, pipe and other goods also must satisfy these requirements.

It is important that also the plastic material that is used to make these containers, pipe and other goods should be very solid, make the goods of making by this plastic material have enough intensity.And for economic reasons, require so any plastic material to be easy to make commercial salable container, pipe or other goods, or easy improved production machinery.When the workability of any plastic material that is identified for making this series products, such as production rate, stability of material, particulate produce, the factor of scrap stock rate and possible returns all is the problem that crucial needs are considered.

As mentioned above, since these plastic materials will be processed to the splendid attire medicine or with the contacted flexible cell of medicine and other medical equipment introduced in the human body, so must not containing, these plastics can perhaps do not contained and to enter the intravital chemical of patient with medicine by the chemical of pharmaceutical extraction.For making plastic material softness, the common machinable and stable various additives that are used for polymer formulators are particularly importants.The toxicity of these additives is scopes of important problem and detection.

For such as intravenous infusion bag, Dialysis container, bags of blood, introducing utensil and these medical equipments of pipe, general custom is in adding the thermic sterilization or working by chemostefilant (as ethylene oxide gas).Yet under the situation of thermal sterilization, there is such problem, promptly is used for the heat-resisting degraded of synthetic resins needs of such medical container, pipe and other goods.Under with ethylene oxide gas disinfectant situation, such problem is arranged, after sterilization, the medicament reservoir that is sterilized, pipe and other goods do not contain before the ethylene oxide gas, expend considerable time.As a kind of available method, the someone advises sterilizing with radiation method.Because this method is carried out at low temperatures, the material of medicament reservoir, pipe and other goods no longer needs can heat-resisting and heat-resisting degraded.Yet the radiation meeting causes rotten and such class injurious effects that fade by radiating medicament reservoir, pipe and other goods, unless this plastic material is suitably made by prescription.

Vinyl chloride-base polymer (" PVC ") has many premium propertiess, and this makes it become one of topmost industrial plastics in the world.In medicine industry, PVC is widely used in and comprises many application intravenous and drug delivery container, Dialysis container, bags of blood, solution introducing utensil, pipe and other moulded parts.For these medicinal uses, in the processing of PVC and use, depend on various softening agent, stablizer and other additive, and this is under the situation of accepting the harmful performance of some other potential.For example, flexible IV container requires it to have low extract, low absorption, the low dizzy degree of water temperature, low colourity and transparency usually.Foundation shortens process period, lowers the wearing and tearing of equipment, does not have particulate matter, hangs down scrap stock rate and high returns rate, in order to improve the processibility of PVC, uses softening agent, stablizer and other additive in making processes.Finally, the PVC container all must be stable in manufacturing, processing and use.

People generally acknowledge that the weakness of PVC is in processing and the thermolability in using, and the result causes dehydrochlorination and conjugated nonsaturation, and causes fadedness to increase with the increase of conjugate length.The mixture of the stablizer by adding some selection can delay thermal destruction, typical stablizer comprises calcium soap, zinc soap, organo-tin compound, comprise the dialkyl tin ester, as alkyl carboxylic acid ester (as laurate and stearate), dioctyltin maleic acid ester polymkeric substance and dioctyltin-S, S '-two (iso-octyl) mercaptoacetate, epoxidized fatty acid ester and organophosphite.

In order to satisfy the desired low extractable of these medical containers, pipe and other goods, because stabiliser content is low, the degraded of PVC and may run into the difficulty of stability and processing aspect.Yet this low stabiliser content is had opposite useful effect by the minimizing of the water extractable matter of PVC film.When the more extract of tolerable, or the stability of PVC is when more important, can use more processing aid and stablizer, yet, known extrude with molding technology in, may run into that the incrustation of overlubricate agent or crosslinked (solidified) epoxide and other processing aid accumulate and the processing difficulties that causes on mould and chill roll equipment.

The invention provides the additive system that is used for PVC prescription functional performance with the further medical equipment that improves processibility and make by PVC.With regard to the fusion manufacturing of PVC and thermostability (as having improved thermostability, and colour-fast or form black particle for fast fast thawing stream in the extrusion; Incrustation or the accumulation of minimizing on processing units; Reduce scrap stock and equipment downtime, increase the use of returns) and required product performance (water temperature is dizzy for for example low colourity, optical haze degree, extract and produce particle) and opinion, these additive systems surpass the system of previously known surprisingly.

Additive system of the present invention comprises main stabilizer and co-stabilizer and external lubricant.Additive system of the present invention preferably includes the zinc salt main stabilizer of optimum amount and the mixture of epoxide co-stabilizer and polyethylene external lubricant.Also can comprise other processing aid and performance additive such as alkali (being magnesium oxide, dihydro white mica, lime carbonate), oxidation inhibitor (being sterically hindered phenol and amine, organophosphite or phosphonic acid ester), tinting material, biocide and internal lubricant.

These additive systems can be used for the application of rigidity, semi-rigid or flexible PVC.For example, additive system of the present invention provides stability and processibility to the low plasticising or the unplasticizied PVC prescription of injection moulding, with production rigidity or semi-rigid product, as strainer consent and drop container.Equally, additive system of the present invention also provides stability and processibility, this prescription generally to be used for producing to plastifying PVC prescription to be used for such as this class fluidic flexibility IV container of intravenous solution, peritoneal dialysis solution, blood and blood products.Common known softening agent comprises phosphate dialkyl ester, three mellic acid trialkyl esters, phenylformic acid alkyl or aryl ester, citrate, and polymeric softening agent, as urethane, ethane-acetic acid ethyenyl ester and-trimer of carbonoxide, and polyester.

The preferred embodiments of the invention will be described in detail supplementary features of the present invention and advantage, and these feature and advantage are conspicuous.

The invention provides the additive system of PVC prescription, medical container, tubular equipment and the moulded parts made from the further processibility of improving material with by such material functional.The composition of preferred additive system of the present invention comprises the advocate peace co-stabilizer and the external lubricant of optimum quantity, and wherein main stabilizer is the Lewis acid metallic compound, and it stops the extraction of aqueous fluid from the PVC plastics.

The main stabilizer of optimum quantity is selected from organo-tin compound, comprises the ester of dialkyl tin, as alkyl carboxylic acid ester (as laurate and stearate), and dioctyltin maleic acid ester polymkeric substance and dioctyltin-S, S '-two (iso-octyl) mercaptoacetate; Organic zinc compound, comprise the alkyl carboxylate, as zinc salts of fatty acids (lauroleate, palmitate, stearate, eruciate ， docosoic salt, abietate etc.), and based on monomer (as ethene, alkyl acrylate, or vinylbenzene and vinylformic acid, fumaric acid or toxilic acid etc.) zinc salt of superpolymer of polymerization of mixtures.This group main stabilizer does not comprise the metal ion of I A in the periodictable or II A family, and plastic formula produced water temperature and swoons when known their use of people will cause in being exposed to water (liquid or steam).For example, zinc plays the Lewis acid liquefying agent, removes unsettled gas among the PVC, but also at melt polymer body and melt-processed equipment surface initiated polymerization and make the ethylene oxide group of epoxide co-stabilizer crosslinked (being discussed below).The main stabilizer amount ranges is that per 100 parts of polyvinyl chloride resins (" phr ") contain 0.02-0.5 part in the PVC prescription.Preferred main stabilizer is a Zinic stearas, and preferred amount is about 0.05-0.3phr.The advantage of Zinic stearas is before with steam, oxyethane or radiation sterilization and can both provides high optical transparency afterwards.

Co-stabilizer of the present invention is selected from the group of being made up of epoxide, and it and PVC have good consistency with other system component, provides PVC the stability of prescription with activation.Many epoxide still are the good softening agent of PVC, and some is the unique and main softening agent that is applicable to this prescription.These epoxide can use separately or mix arbitrarily and use.Suitable epoxide includes but not limited to glycerine three (Epoxy oil acid esters), low epoxidised Semen Lini oil of ethylene oxide content or soya-bean oil, or partially hydrogenated polyunsaturated vegetable oil, propylene glycol two (Epoxy oil acid esters), the multipolymer of Racemic glycidol oxypropylene acid esters.The co-stabilizer per molecule contains less than about 5.2 oxyethane.According to the needs that prescription is used, the amount ranges of co-stabilizer in the PVC prescription is 5-100 phr.For example, if additive system joins among the plastifying PVC, then the preferable range of co-stabilizer is about 10-20phr for flexible application (being flexible medical container).For flexible application, if additive system joins among the PVC of non-plasticizing, then preferable range is about 40-80phr equally.In the present invention, preferred co-stabilizer is propylene glycol two (an Epoxy oil acid esters), and per molecule generally contains 2.5 oxyethane.And, have been found that in PVC when prescription that obtains the aqueous solution, biofluid and cell tissue are had low extractibility, the purity of epoxide is an important factor.

For the actual manufacturing (as product of the present invention) of PVC prescription, melt-processed is necessary.External lubricant provides the slip with respect to the metal of processing units, with separating from the metal of processing units; For example, film extruder screw, mould and film cooling roller, or injection screw, geat and runner.The concrete advantage that is used for this lubricant of film extrusion molding is: (ⅰ) melt-flow speed is very fast, the by product that (ⅱ) degraded of less heat and shear-stress causes fading, black splotch, lower molecular weight and more water can extract, (ⅲ) prevent from the mould drag line, what (ⅳ) prevent that degrade and crosslinked material from causing in accumulation on the die lip has a loose granule on film, film is less simultaneously is adhered on the cooling roller, and finished product itself is bonding also less.Yet, the concentration of lubricant must be by balance delicately to reach these advantages, and do not have excessive lubricant to cause that poor melts transports (for example extruding), the accumulation (drag line, the loose granule that do not have lubricant " incrustation " on mould and extrusion apparatus, with material in the degraded on the film) and less than the accumulation (loose granule is arranged on film) at " incrustation " on the cooling roller.

Because other each component of external lubricant and melt polymerization composition formula is incompatible, therefore during processing, on the surface of flowing melt, the common external lubricant in the PVC prescription is concentrated.Epoxide stabilizer and metal complex stablizer (and by product) are prevailing stablizers among the PVC because they are lower with respect to PVC viscosity, so on the surface of the melt that flows they also by rheology concentrate.The enriched mixture that epoxide, metal complex by product, lubricant and protonic acid (from the dehydrochlorination of PVC and subsequently neutral HCl and carboxylic acid by the carboxylicesters soap of stabiliser system) therefore, arranged at the bath surface that flows.Therefore, epoxide polymerization, crosslinked and be adhered to the metallic surface of processing units, and mix with external lubricant, bath surface attracts lubricant from flowing.

The reactive behavior of viscosity, concentration, quantity and oxyethane that the intensity of this dirt settling accumulation and degree not only depend on these components, but also depend on polymerizable molecular amount and cross-linking density, by the ratio of epoxide and initiator (acid or alkali) concentration, the quantity of Oxyranyle and they are determined near the degree (being the oxyethane equivalent of epoxide) of epoxide again for itself.Therefore, epoxide and initiator have an optimum proportion.When suitable stability of material is provided, incrustation is cut to bone under this ratio, and extractibility is low when using with water-based fluid.

Being used for external lubricant of the present invention comprises: for example, the polyethylene of polyethylene, oxidation, polyethylene ionomer, poly-hydrofluoric ether (for example contain TFE, FEP, VF ₂, perfluor ether polymkeric substance), paraffin, ester type waxes, amide waxe, poly-(ethyleneether), the multipolymer of oxyethane and propylene oxide, polymeric amide, polypeptide, poly-(vinyl alcohol), poly-(ethene-CO-vinyl alcohol), poly-(hydroxy alkyl ester of vinylformic acid and methacrylic acid), the multipolymer of vinylformic acid or its salt, maleic anhydride and ethene, propylene or cinnamic multipolymer contain the multipolymer of sulfonic group and salt thereof, and sulfonated poly-(fragrant sulfone).Preferred lubricant of the present invention is stable between processing and usage period, and does not pollute medicine and biological substance when contacting with the PVC prescription.Each lubricant can use or mix use separately, as long as determine the optimum value of concentration and epoxide and initiator (acid or alkali, adding or by the by product generation) ratio by foregoing.

FOR ALL WE KNOW, the performance of PVC prescription of the present invention depends on the amount of advocate peace co-stabilizer and external lubricant and the proper equilibrium between the character.For obtain low colourity, low extract and on the metal-working plant surface incrustation hardly, the proper equilibrium of stablizer and lubricant is especially necessary.With acid or base catalyzed polymerization, and epoxide is surface-crosslinked at fusion PVC prescription in melt-processed (i.e. batching or secondary processing) process, all may cause incrustation, above-mentionedly crosslinkedly cause that the strong epoxide of the metallic surface that external lubricant contacts with melt is bonding.This bond strength depends on the molecular weight and the cross-linking density of polymeric epoxide, this is a maximum value when the stoichiometric ratio of certain centre of epoxide and acid or alkali initiator for this intensity, these initiators are strong lewis acid by products of main stabilizer (for example muriate of tin or zinc) for example, or the excesses of basic of acidproof buffer reagent (for example magnesium oxide particle).

Therefore, prevent or this incrustation reduced to minimum, thereby reduce the influence of the discrete particle that in the fluid that comprises that contact with frosting, finds that this is usually to break because of incrustation to leave processing units and loosely turns back on the frosting.And avoid incrustation can prevent that also the PVC goods from being polluted by the particle (normally black splotch) that the incrustation of the degraded of the height on the hot metal surface of melt-processed equipment discharges.Utilize this theory, we can prevent even epoxide had incrustation on easy to be out of order surface reactive behavior and that have high surface energy (general about 40 dynes per centimeter), as be used for the common stainless steel metal oxide surface that the plasticized PVC prescription is made in fusion.This explanation is supported in the analysis of the extrusion molding of viewed PVC compound composition of the present invention and injection mould goods and incrustation thing.

The high-density linear polyethylene of contour melt viscosity during the preferred embodiments of the invention are used, it accounts for about 0.015% weight in PVC prescription, and with about 9.1% weight propylene glycol pair (Epoxy oil acid esters) and about 0.063% weight Zinic stearas (stearic acid buffered) with its stabilization.When with about 28% weight terephthalic acid ethylhexyl plasticising, have the form that the PVC prescription of this preferable additives system can film and extrude at a high speed, and do not have incrustation, fade, black particle or discrete particle.And, but contain the PVC prescription injection molding of preferable additives system, and do not fade, black particle or sticking to mould.Contain that goods that the PVC of this preferable additives system makes are can be with radiation, steam or oxirane disinfection within reason to fade, produce extract or toxicity.And the PVC that contains this preferable additives system provides flexible cell for medical and biological liquid, and they still keep transparent especially (for example temperature is swooned or permanent optical haze hardly) after with steam sterilizing.

The several method between the film sample of the commercially available PVC prescription of the film sample of the preferred embodiment of the invention and other and the comparison of function test, be reported in table 1 and 2 and Fig. 1-5 in.The equivalent terephthalic acid ethylhexyl plasticising of the film sample of each test.What table 1 illustrated is the additive system of preferred embodiment and the comparison of other each component of PVC formulation additives system.

Table 1

The additive system of plastifying PVC material ¹

Stablizer Comparative Examples 1 ²Comparative Examples 2 ²Comparative Examples 3 ³Comparative Examples 4 ²Embodiment ³

Main stabilizer

Zinc stabilizer

Zinic stearas-calcium * *

Zinic stearas * * *

Co-stabilizer

Epoxide

About 5.2 oxyethane/molecule * *

About 2.5 oxyethane/molecule * * *

Lubricant

Ethylenebis (stearylamide) * *

High density polyethylene(HDPE) * * *

Incrustation/accumulation ⁴Do not have and have or not

Particulate matter ⁵Have or not

1. each sample material contains the terephthalic acid ethylhexyl

2. contain about 0.2phr or more main stabilizer

3. contain main stabilizer less than 0.2phr

4. on extrusion dies and chill roll, occur during the processing

5. black splotch generally appears during processing

Table 2

Test subject UV@ UV@ zinc oxide △ pH ammonia

220nm??241nm??(ppm)??(ml)??(ppm)

Tolerance 0.08a.u. 0.05a.u. NMT0.5 NMT1.0ml NMT1.0 NMT0.5

Embodiment

Organize 1 roller A 0.051 0.031 0.27 0.48-0.74＜0.5

Roller B 0.057 0.031 0.26 0.38-0.82＜0.5

Organize 2 roller A 0.054 0.027 0.24 0.40-0.73＜0.5

Roller B 0.055 0.029 0.24 0.40-0.80＜0.5

Organize 3 roller A 0.048 0.027 0.26 0.45-0.82＜0.5

Roller B 0.043 0.026 0.26 0.40-0.82＜0.5

Embodiment W/30% returns

Organize 1 roller A 0.048 0.029 0.27 0.52-0.84＜0.5

Roller B 0.051 0.029 0.26 0.38-0.84＜0.5

Comparative Examples 3

Organize 1 roller A 0.046 0.030 0.12 0.32-0.65＜0.5

Roller B 0.053 0.034 0.11 0.36-0.57＜0.5

Comparative Examples 4

Organize 1 roller A 0.031 0.027 0.59 0.5-0.40＜0.5

Roller B 0.027 0.027 0.61 0.35-0.2＜0.5

Just the feature progression of the color that presents at heated PVC (transparent, colourless, to yellow, to orange, to redness, to brown) signifying to develop more and more the system of long conjugated polyene sequence.PVC even also very sensitive to slight heating, forming the visible color usually at first is the distinguishing mark of degraded.These variations have just taken place before any more serious signs of degradation becomes obviously.Will produce physical change if continue heating.

Static heating (baking oven) and the test of dynamic heat (Brabender) colour stability provide and have early produced the indication of color to dehydrochlorination.These stability tests are with approaching with observed signs of degradation in the currently known methods extrusion molding PVC thin-film process.

The yellowness index that contains the sample film of the definite additive system of table 1 by mensuration is determined thermostability.Film sample bar is placed in 370 (188 ℃) air circulation ovens, for testing regular taking-up sample strip.Use can be measured yellowness index with known technology from the colorimeter that Hunter company buys.The yellowness index result relevant with static heat stability makes in Fig. 1.Estimate these sample film, the film (embodiment) that comprises the preferable additives system demonstrates best colour stability in the whole time.And, comprise the film of preferred additives system and present identical static heat stability with film with 30% reclaimed materials production.

Fusion and shearing PVC material in Brabender fusion head, initial air causes dehydrochlorination reaction, causes color to be degraded gradually.The dehydrochlorination back is crosslinked, and viscosity obviously increases, the darkening and shockingly blackening of PVC material.Brabender test is different from when being heated to specific temperature the heat ageing test that shearing force is applied on the material.Therefore, the result of Brabender test not only depends on thermostability, but also depends on the fusion oilness that is produced by each component of prescription.This is with to make the PVC material be in the condition of melt-processed process such as extrusion molding and injection moulding very approaching.Simultaneously, the rim charge that grinds and the reuse of returns may cause the PVC material to be subjected to additional heat and fusion shear-stress.Therefore this test can be used for simulation returns is added to extruding machine or injection moulding machine, repeated multiple times with unworn material.

Mensuration comprises the yellowness index of the PVC film sample of the definite various additive systems of table 1.With reference to figure 2, best film sample is with known extrusion molding production (operation number=0).Then that this is initial sample is handled 20 minutes (operation number=1) with 370 °F (188 ℃) 60 rev/mins in air in Brabender equipment.With containing 70% initial film and 30%, carry out the reuse of 4 (by number=2,3,4,5) returns from the sample of the returns of sample formerly at once.For example, the sample of operation numbers 2 is that 70% initial film and 30% is from the returns of operating number 1 sample.The yellowness index result makes in Fig. 2.Under the identical processing conditions of general known extrusion molding (adding the contamination of hot shearing and returns), the film sample that comprises the preferable additives system has shown best colour stability.

And, the optimum concn that we have known main stabilizer (preferred Zinic stearas) and co-stabilizer epoxide [preferred propylene glycol two (Epoxy oil acid esters)] to the thermostability of PVC material and processibility generation surprising with unexpected improvement.By formula (1) uses Zinic stearas (Znst ₂Replace unsettled hydrochloric ether on PVC, to react, and by formula in (2) and hydrochloric acid.

With reference to figure 3, the excessive concentration of Zinic stearas (for example Comparative Examples 4) will make zinc chloride increase, and this is with degraded and the dehydrochlorination of further catalysis PVC.We find that excess chlorination zinc also plays a part the cross-linked evocating agent of epoxide, and this causes and produce a large amount of incrustation in extrusion process, and produces black particle during extrusion molding and injection moulding.By this way, excess chlorination zinc also will exhaust oxyethane, further cause the loss of stability.Otherwise if stearic acid zinc concentration too low (for example Comparative Examples 3) PVC is attended by by product HCl with dehydrochlorination, this will speed up this degradation process and causes crosslinked consumption oxyethane.

Because in and HCl(formula 3) therefore and make the less prescription of zinc chloride (formula 4), so the stability that the epoxide of appearance by optimum quantity causes.

X is-OH or stearate in the formula.

But the excessive concentration of epoxide can obviously not improve colour stability, but because the initiation of the acid that is produced in the heat-processed causes epoxide more crosslinked.On the contrary, the epoxide of lower concentration will promptly be consumed, and therefore be not enough to the protection that provides stable.

By using the preferred additives system, further processing effect and saving have been realized.Point out as table 1 we find that surprisingly material can incrustation or accumulation on processing units when using additive system of the present invention.Therefore, can not cause incrustation, in the stop time that does not have incrustation on the extrusion dies and on chill roll, do not have accumulation just to save extrusion apparatus in order to improve melt-processed can use the lubricant of high level.And, during processing, can in melt-processed equipment, not accumulate and produce the black particle material.With present available PVC material relatively, the scrap stock rate can reduce about 20-30% when using additive system of the present invention.

With the product that the PVC material that comprises additive system of the present invention is made, realized the improvement of product performance.For example, the extract of medical container, mouth and the pipe that makes with this PVC material is less, and has improved with the transparency after the steam sterilizing.Below Japanese Pharmacopoeia XII disquisition (JP XII) medical container of the PVC prescription of the various additive systems that contain table 1 and list and the extract in the extruded film material are detected.Film sample is cut into inch strips, and presses heat 1 hour at 121 ℃ in 200 milliliters of distilled deionized waters.For the existence of zinc, ammonia and oxide compound, pH changes and the UV absorbing material (241 and the 220nm wavelength), analyze water extract.

The JP XII extract data that are with or without the mould material sample of returns are listed in table 2, and the result confirms to contain the thin-film material of PVC additive system of the present invention in the tolerance deviation directrix of JP XII standard.And, will contain the mould material of PVC additive system of the present invention and the water extract of other PVC film and compare, Fig. 4 provides oxide compound relatively, and Fig. 5 provides the comparison of UV absorbing material.

Though the various changes and modifications to described herein preferred embodiment concerning the those of skill in the art in present technique field are conspicuous.For example, can predict as being used for PVC additive system of the present invention and can be used for chlorinatedpolyolefins, as chlorinatedpolyethylene and polypropylene, these changes and improvements do not break away from thought of the present invention and scope, and do not reduce the advantage that it had.Therefore plan with topped these changes and improvements of dependent claims.

Claims

1, a kind of additive system that is used for the polyvinyl chloride prescription is used to improve processibility when keeping this prescription thermostability, and this additive system comprises:

A kind of main stabilizer: be the Lewis acid metallic compound that is selected from organo-tin compound and organic zinc compound;

A kind of co-stabilizer: be selected from the epoxide that is less than about 5.2 Oxyranyles in the per molecule; With

A kind of external lubricant of significant quantity is used for the lubricated of PVC prescription;

Wherein the ratio of main stabilizer and co-stabilizer is increased to hot colour stability to greatest extent, is limited in the generation of accumulation, incrustation and black particle too much in the polyvinyl chloride prescription course of processing simultaneously.

2, by the additive system of claim 1, wherein main stabilizer is that its amount of Zinic stearas is, per 100 parts of polyvinyl chloride contain about 0.02-0.5 part.

3, by the additive system of claim 1, wherein co-stabilizer is propylene glycol two (an Epoxy oil acid esters), and its amount contains about 5-100 part for per 100 parts of polyvinyl chloride.

4, by the additive system of claim 1, wherein external lubricant is a high density polyethylene(HDPE).

5, a kind of additive system that is used for the polyvinyl chloride prescription is used to improve processibility when keeping this prescription thermostability, and this additive system comprises:

A kind of main stabilizer: be a kind of Lewis acid metallic compound that is selected from organo-tin compound and organic zinc compound, its amount contains about 0.02-0.5 part for per 100 parts of polyvinyl chloride;

A kind of co-stabilizer: be selected from the epoxide that is less than about 5.2 ethylene oxide groups in the per molecule, its amount contains about 5-100 part for per 100 parts of polyvinyl chloride; With

A kind of external lubricant that is used for lubricated polyvinyl chloride prescription of significant quantity.

6, by the additive system of claim 5, wherein main stabilizer is an organo-tin compound, is selected from the ester of dialkyl tin, dioctyltin maleic acid ester polymkeric substance and dioctyltin-S, S '-two (iso-octyl) mercaptoacetate.

7, press the additive system of claim 5, wherein main stabilizer is an organic zinc compound, be selected from alkyl carboxylic ester, comprise zinc salts of fatty acids and based on the zinc salt of the polymer ionomer of the mixture of monomer ethylene, alkyl acrylate or vinylbenzene and vinylformic acid, fumaric acid or toxilic acid.

8, by the additive system of claim 5, wherein main stabilizer is a Zinic stearas.

9, by the additive system of claim 5, co-stabilizer per molecule 2.5 oxyethane of having an appointment wherein.

10, by the additive system of claim 5, wherein co-stabilizer is propylene glycol two (an Epoxy oil acid esters).

11, press the additive system of claim 5, wherein external lubricant is selected from polyethylene, oxidic polyethylene, polyethylene ionomer, poly-hydrofluoric ether, paraffin, ester type waxes, amide waxe, the multipolymer of poly-(ethyleneether), oxyethane and propylene oxide, polymeric amide, polypeptide, polyvinyl alcohol, poly-(ethene-CO-vinyl alcohol), the multipolymer of poly-(acrylic acid hydroxy alkyl ester and hydroxyalkyl methacrylate), vinylformic acid or its salt, maleic anhydride and ethene, propylene or cinnamic multipolymer, the polymkeric substance and the sulfonated poly-(fragrant sulfone) that contain sulfonic group and salt thereof.

12, by the additive system of claim 5, wherein external lubricant is a high-density linear polyethylene.

13, by the additive system of claim 5, wherein the amount of main stabilizer is that per 100 parts of polyvinyl chloride contain about 0.05-0.3 part.

14, by the additive system of claim 5, wherein the amount of co-stabilizer is that per 100 parts of polyvinyl chloride contain about 10-20 part.

15, by the additive system of claim 5, wherein the amount of co-stabilizer is that per 100 parts of polyvinyl chloride contain about 40-80 part.

16, the pharmaceutical prod of producing by the polyvinyl chloride prescription that contains additive system, this additive system comprises:

The main stabilizer of about 0.06% weight is a kind of Lewis acid metallic compound that is selected from organic zinc compound;

The co-stabilizer of about 9.1% weight is selected from the epoxide that is less than about 5.2 Oxyranyles in the per molecule; With

The external lubricant of about 0.015% weight.

17, by the pharmaceutical prod of claim 16, this product is to pass through the extrusion molding processing by this polyvinyl chloride prescription that contains additive system.

18, by the pharmaceutical prod of claim 16, this product is by the polyvinyl chloride prescription that contains this additive system injection moulding processing.

19, by the pharmaceutical prod of claim 16, wherein this product is used for the splendid attire aqueous solution, biofluid and cell tissue.

20, by the pharmaceutical prod of claim 16, wherein this product is a tubular products.